Fluorenyl-containing polymeric metallocene catalyst systems

ABSTRACT

A catalyst system comprising an organoaluminoxane cocatalyst and a polymeric fluorenyl-containing metallocene prepared from a polymer resulting from the polymerization of a 2-vinylfluorene compound or the alkylation of a fluorene compound.

This application is a Division of application Ser. No. 08/339,537, filedNov. 15, 1994, now U.S. Pat. No. 5,770,755.

The present invention relates to polymeric ligands, polymericmetallocenes, catalyst systems, processes for preparing same, and olefinpolymerization processes.

BACKGROUND OF THE INVENTION

Metallocene catalysts have been used in homogeneous solutionpolymerizations. Attempts to use soluble metallocene catalysts in aslurry or particle form type polymerization are currently notcommercially feasible. It has been observed that when such particle formpolymerizations are carried out in the presence of a soluble metallocenecatalyst, large amounts of polymeric material are formed on the surfacesof the polymerization vessel. This fouling produces an adverse effect onthe heat transfer and also results in the need for periodic, if notcontinuous, cleaning of the reactor.

It would therefore be desirable to produce economical metallocenecatalysts useful in polymerization processes free of reactor fouling.

For many applications, such as thermoforming, extrusion, blow moldingand the production of film, it is desirable to produce a polymer havinga broad molecular weight distribution.

It would therefore be desirable to produce metallocene catalysts capableof producing polymers having a broad molecular weight distribution.

Another important characteristic of polymers is the environmental stresscrack resistance, which can be improved by the incorporation ofcomonomer in the high molecular weight portion of polymers having abroad molecular weight distribution.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a polymeric liganduseful in preparing polymeric metallocenes.

Another object of the present invention is to provide an economicalprocess for preparing a polymeric ligand.

Another object of the present invention is to provide a polymericmetallocene useful in olefin polymerization which does not producesignificant reactor fouling in a particle form polymerization process.

Another object of the present invention is to provide mixtures ofpolymeric metallocenes useful in preparing polymers having a broadmolecular weight distribution.

Another object of the present invention is to provide mixtures ofpolymeric metallocenes useful in preparing polymers having improvedenvironmental stress crack resistance.

Another object of the present invention is to provide an efficient andeconomical process for preparing polymeric metallocene catalysts.

Still another object of the present invention is to provide apolymerization process free of significant reactor fouling, especiallyin particle form processes.

In accordance with the present invention, polymeric ligands, polymericmetallocenes, catalyst systems, processes for preparing same, andpolymerization processes are provided. The process for preparingpolymeric metallocenes comprises reacting a polymeric ligand, an alkalimetal compound, and a transition metal-containing compound, wherein thepolymeric ligand contains a cyclopentadienyl-type group, as hereinafterdefined, wherein the transition metal-containing compound is representedby the formula MX₄ wherein M is a transition metal, and each X isindividually a hydrocarbyl group containing 1 to 20 carbon atoms, analkoxy group containing 1 to 12 carbon atoms, an aryloxy groupcontaining 6 to 20 carbon atoms, a halide, or hydride. In anotherembodiment, a process for preparing polymeric ligands comprises reactingat least one bridged cyclopentadienyl-type monomer, as hereinafterdefined, and an initiator under polymerization conditions. In anotherembodiment, polymeric ligands are represented by the formula [Q']_(n),wherein Q' is a unit containing at least one bridgedcyclopentadienyl-type group and wherein n is 1-5000. Polymeric ligandscomprising mixtures of bridged and unbridged cyclopentadienyl-typegroups are also provided. In another embodiment, polymeric metallocenesare represented by the formula [Q"MX_(m) ]_(n), wherein Q" is a unitcontaining at least one fluorenyl-type group, as hereinafter defined, Mis a transition metal, each X is individually a hydrocarbyl groupcontaining 1 to 20 carbon atoms, an alkoxy group containing 1 to 12carbon atoms, an aryloxy group containing 6 to 20 carbon atoms, ahalide, or hydride, m is 2 or 3, and wherein n is 1-5000. The catalystsystems comprise the polymeric metallocene and an organoaluminoxane. Thepolymerization process comprises contacting the catalyst system and atleast one olefin under polymerization conditions.

DETAILED DESCRIPTION OF THE INVENTION

A process for preparing polymeric metallocenes comprises reacting apolymeric ligand, an alkali metal compound, and a transitionmetal-containing compound.

Polymeric Ligand

The polymeric ligand employed in preparing the polymeric metallocene isrepresented by the formula [Q]_(n), wherein Q is a unit containing atleast one cyclopentadienyl-type group and wherein n is 1-5000,preferably 3-1000. Cyclopentadienyl-type, as used herein, includesgroups containing a cyclopentadienyl functionality, and includescyclopentadienyl, substituted cyclopentadienyl, indenyl, substitutedindenyl, fluorenyl and substituted fluorenyl groups. Fluorenyl-typegroups are preferred. Fluorenyl-type as used herein includes groupscontaining a fluorenyl functionality, and includes fluorenyl andsubstituted fluorenyl containing compounds. Typical substituents for theabove defined cyclopentadienyl-type groups include hydrocarbyl groupscontaining 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, alkoxygroups containing 1 to 12 carbon atoms, or halide. Preferably thesubstituents are alkyl groups containing 1 to 10 carbon atoms, morepreferably 1 to 6 carbon atoms. Some examples of substituents includemethyl, ethyl, propyl, butyl, tert-butyl, isobutyl, amyl, isoamyl,hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl,pentenyl, butenyl, phenyl, chloride, bromide, and iodide.

Examples of typical cyclopentadienyl-type groups include fluorene,vinylcyclopentadiene, (1-methylethenyl)cyclopentadiene,(1-(4-vinyl)phenyl)cyclopentadiene, penta-2,4-dienylcyclopentadiene,2-vinyl-7-methylfluorene, 1-vinyl-3-butylcyclopentadiene,2,7-dimethyl-9-vinylfluorene, 1-vinylindene, 2-vinylindene,3-vinylindene, 4-vinylindene, 5-vinylindene, 6-vinylindene,7-vinylindene, 1-vinylfluorene, 2-vinylfluorene, 3-vinylfluorene,4-vinylfluorene, 5-vinylfluorene, 6-vinylfluorene, 7-vinylfluorene,8-vinylfluorene, 9-vinylfluorene, and mixtures thereof.

The term polymeric, as used herein, is intended to include bothhomopolymers and copolymers. Copolymers can include mixtures ofcyclopentadienyl-type groups and/or other polymerizable monomers. Theterm polymerization, as used herein, is intended to include bothhomopolymerization and copolymerization. The term monomer, as usedherein, refers to a compound capable of undergoing polymerization.

In addition to the at least one cyclopentadienyl-type group, the unit Qcan also contain other groups, such as styrene. When styrene isemployed, the relative amount of styrene and cyclopentadienyl-type groupcan vary broadly depending on the particular results desired. Generally,when employing a styrene comonomer, the styrene will be present in anamount in the range of from about 0.1 mole to about 5000 moles styreneper mole of cyclopentadienyl-type group, preferably styrene is presentin the range of from about 0.1 mole to about 1500 moles styrene per molecyclopentadienyl-type group, and more preferably from 1 mole to 1000moles styrene per mole cyclopentadienyl-type group.

The polymeric ligands can be prepared by any method known in the art.Examples of some such methods are disclosed in U.S. Pat. No. 3,079,429,Journal of Polymer Science: Polymer Chemistry Edition, Vol. 23,1433-1444 (1985), and Journal of Polymer Science, Polymer letters, Vol.9, 671-676 (1971), the disclosures of which are incorporated herein byreference.

One method for preparing the polymeric ligand involves radicalpolymerization by reacting an initiator and at least onecyclopentadienyl-type monomer under polymerization conditions. Suitableinitiators include azobisisobutyronitrile, phenyl-azo-triphenylmethane,tert-butyl peroxide, cumyl peroxide, acetyl peroxide, benzoyl peroxide,lauroyl peroxide, tert-butyl hydroperoxide, and tert-butyl perbenzoate.The method is also effective when employing styrene as comonomer.Generally the reaction is conducted in the presence of a diluent such astoluene. Generally conditions suitable for the radical polymerization ofthe cyclopentadienyl-type monomer will include a temperature in therange of from about 0° C. to about 150° C.

Another method for preparing the polymeric ligands involves cationicpolymerization by reacting an initiator, such as boron trifluorideetherate, and a cyclopentadienyl-type monomer under polymerizationconditions. Generally the reaction is conducted in a diluent such asmethylene chloride. The method is also effective when employing styreneas comonomer. Suitable cationic polymerization conditions for preparingthe polymeric ligand include a temperature in the range of from about-80° C. to about 0° C.

Still another method for preparing the polymeric ligands involvesalkylating polymerization by reacting zinc dichloride or aluminumtrichloride and a cyclopentadienyl-type monomer in chloromethyl methylether under polymerization conditions. Suitable aluglatingpolymerization conditions for preparing the polymeric ligand include atemperature in the range of from about -20° C. to about 50° C.

Another method for preparing the polymeric ligands involves anionicpolymerization by reacting an alkali metal compound and acyclopentadienyl-type monomer under polymerization conditions. Generallythe reaction will be conducted in a diluent such as diethyl ether.Suitable conditions for anionic polymerization include a temperature inthe range of from about 0° C. to about 150° C., preferably from about 0°C. to about 100° C., and more preferably from 0° C. to 50° C.

Alkali metal compounds suitable for preparing the polymeric ligand byanionic polymerization are represented by the formula AR', wherein A isan alkali metal selected from the group consisting of lithium, sodium,and potassium and wherein R' is a hydrocarbyl group selected from thegroup consisting of alkyl, cycloalkyl, and aryl groups containing 1 to12 carbon atoms. Preferably R' is an alkyl group containing 1 to 10carbon atoms. Lithium alkyls containing 1 to 8 carbon atoms areespecially preferred. Examples of preferred lithium alkyls includemethyllithium, ethyllithium, propyllithium, butyllithium, pentyllithiumand hexyllithium. Excellent results have been obtained withn-butyllithium and it is especially preferred. The alkali metal compoundis generally present in an amount in the range of from about 0.1 mole toabout 20 moles alkali metal compound per mole cyclopentadienyl-typemonomer, preferably about 0.2 mole to about 10 moles, and morepreferably about 0.5 moles to about 5 moles alkali metal compound permole cyclopentadienyl-type monomer.

Bridged Polymeric Ligand

In one embodiment of the invention, a bridged polymeric ligand isprovided. The bridged polymeric ligand is represented by the formula(Q'). wherein Q' is a unit containing at least one bridgedcyclopentadienyl-type group and wherein n is 1 to 5000, preferably3-1000. The bridged cyclopentadienyl-type group is represented by theformula ZRZ, wherein each Z is individually a cyclopentadienyl-typegroup, and R is a bridging group and is an alkylene group containingfrom 1 to 12 carbon atoms, an aryl-containing group having from 6 to 12carbon atoms, silicon-containing group, germanium-containing group, ortin-containing group. Preferably R is an allylene group containing 1 to10 carbon atoms.

Typical examples of bridged cyclopentadienyl-type monomers are1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane,

(9-(2-vinyl)fluorenyl)(cyclopentadienyl)methane,

(9-fluorenyl)(cyclopentadienyl)methane,

1-(9-(2-vinyl)fluorenyl)-2-(cyclopentadienyl)ethane,

(9-(2-vinyl)fluorenyl)(1-indenyl)methane,

1-(9-(2-vinyl)fluorenyl)-1-(cyclopentadienyl)cyclopentane,

(9-(2-vinyl)fluorenyl)(cyclopentadienyl)(1-cyclo-3-hexenyl)methane,

(9-(2-vinyl)fluorenyl)(cyclopentadienyl)dimethylmethane,

(9-fluorenyl)[1-(3-vinyl)phenylcyclopentadienyl]diphenylmethane,

(9-(2,7-divinyl)fluorenyl)(1-(3-methyl)cyclopentadienyl)dimethylmethane,

(9-(2-vinyl)fluorenyl)(cyclopentadienyl)silane,

(9-(2-vinyl)fluorenyl)(cyclopentadienyl)dimethylsilane,

(9-(2-vinyl)fluorenyl)(9-fluorenyl)diphenylsilane,

(9-(2-vinyl)fluorenyl)(cyclopentadienyl)dimethylgermane,

(9-(2-vinyl)fluorenyl)(fluorenyl)dimethylstannane,

1-(9-(2-vinyl)fluorenyl)-3-(cyclopentadienyl)propane,

1-(9-fluorenyl)- 1-(methyl)-1-(1-(2-vinylcyclopentadienyl)ethane,

(9-(2,7-diphenylfluorenyl)(1-(3-vinyl)cyclopentadienyl)diphenylmethane,

bis(9-(1-methyl-4-vinyl)fluorenyl)diphenylmethane,

bis(9-fluorenyl)dimethylmethane,(fluorenyl)(cyclopentadienyl)methyl)(1-(4-vinyl)phenyl)methane andmixtures thereof.

The method for preparing the bridged polymeric ligand comprises reactingat least one bridged cyclopentadienyl-type monomer and an initiatorcompound under polymerization conditions.

The bridged cyclopentadienyl-type monomers can be prepared by any methodknown in the art. Examples of such methods are disclosed in Stone et al.in J. Org Chem., 49, 1849 (1984), European Published Application524,624, and U.S. Pat. Nos. 5,191,132 and 5,347,026, the disclosures ofwhich are incorporated herein by reference.

One method for preparing bridged cyclopentadienyl-type monomers involvesreacting a cyclopentadienyl-type compound with an alkali metal compound,and then with a halogenated cyclopentadienyl-type compound. Thehalogenated cyclopentadienyl-type compound can be prepared by reacting alithiated cyclopentadienyl-type compound and an organo halide, such asdibromoethane or dichloromethane.

Alkali metal compounds suitable for preparing the bridgedcyclopentadienyl-type monomer include those defined above for preparingthe polymeric ligand. Lithium alkyls containing 1 to 8 carbon atoms arepreferred. Excellent results have been obtained with n-butyllithium andit is especially preferred. When preparing the bridgedcyclopentadienyl-type monomer, the alkali metal compound is generallypresent in an amount in the range of from about 0.1 mole to about 20moles alkali metal compound per mole cyclopentadienyl-type compound,preferably about 0.2 mole to about 10 moles, and more preferably about0.5 moles to about 5 moles alkali metal compound per molecyclopentadienyl-type compound.

Reaction conditions for reacting the cyclopentadienyl-type compound andthe alkali metal compound to produce the bridged cyclopentadienyl-typemonomer include a temperature in the range of from about 0° C. to about150° C., preferably from about 0° C. to about 100° C., and morepreferably from 0° C. to 50° C.

The at least one bridged cyclopentadienyl-type monomer is reacted with asuitable initiator compound under polymerization conditions to preparethe bridged polymeric ligand. Suitable initiator compounds includeazobisisobutyronitrile, phenyl-azo-triphenylmethane, tert-butylperoxide, cumyl peroxide, acetyl peroxide, benzoyl peroxide, lauroylperoxide, tert-butyl hydroperoxide, tert-butyl perbenzoate, borontrifluoride etherate, alkali metal compounds, zinc dichloride, andaluminum trichloride. Suitable alkali metal compounds include thosedescribed above for preparing the bridged cyclopentadienyl-typemonomers.

Typically the reaction is conducted in diluents similar to thosedescribed above for radical, cationic, alkylating, and anionicpolymerizations. As noted above, typical examples of such diluentsinclude toluene, methylene chloride, chloromethyl methyl ether, anddiethyl ether for the respective polymerization.

When preparing polymeric ligands containing at least one bridgedcyclopentadienyl-type group, the initiator is generally present in anamount in the range of from about 0.0001 mole to about 20 molesinitiator per mole cyclopentadienyl-type monomer, preferably about 0.001mole to about 10 moles, and more preferably about 0.005 moles to about 5moles initiator per mole cyclopentadienyl-type monomer.

Conditions for preparing the polymeric ligand containing at least onebridged cyclopentadienyl-type group vary broadly depending on thereactants employed. Generally the temperature is in the range of fromabout -80° C. to about 150° C. Suitable conditions are similar to thosedisclosed above for radical, cationic, alkylating, and anionicpolymerizations.

The method is also suitable for the copolymerization of mixtures ofbridged and unbridged cyclopentadienyl-type monomers. The term"unbridged" as used herein refers to groups which are not connected by abridging group. The mixtures can be selected so as to prepare catalystsystems capable of producing polymers having a broad molecular weightdistribution and good environmental stress crack resistance. Whenpolymerizing mixtures of bridged and unbridged cyclopentadienyl-typegroups, typically the bridged cyclopentadienyl-type group will bepresent in an amount in the range of from about 0.001 mole to about 1000moles per mole of unbridged cyclopentadienyl-type group, preferably fromabout 0.01 mole to about 100 moles per mole of unbridgedcyclopentadienyl-type group.

The method is also suitable for the copolymerization of at least onebridged cyclopentadienyl-type monomer with styrene or other similarconjugated system. When employing a styrene comonomer, good results havebeen obtained when employing azobisisobutyronitrile as initiator andtoluene as diluent.

Polymeric Metallocenes

The process for preparing polymeric metallocenes comprises reacting thepolymeric ligand, an alkali metal compound, and a transitionmetal-containing compound.

The polymeric ligand contains a cyclopentadienyl-type group and can beprepared by any method described above.

The transition metal-containing compound is represented by the formulaMX₄, wherein M is a Group IVB or VB transition metal, preferably M iszirconium, hafnium, titanium, or vanadium, more preferably zirconium,haflium, or titanium, and wherein each X is individually a hydrocarbylgroup containing 1 to 20 carbon atoms, preferably 1 to 16 carbon atoms,an alkoxy group containing 1 to 12 carbon atoms, preferably 1 to 8carbon atoms, an aryloxy group containing 6 to 20 carbon atoms,preferably 6 to 12 carbon atoms, a halide, preferably chloride, orhydride. Preferably X is a halide or a cyclopentadienyl-type group.

Alkali metal compounds suitable for preparing the polymeric metalloceneinclude those defined above for preparing the polymeric ligand. Lithiumalkyls containing 1 to 8 carbon atoms are preferred. Excellent resultshave been obtained with n-butyllithium and it is especially preferred.

In preparing the polymeric metallocene, the alkali metal compound isgenerally present in an amount in the range of from about 0.1 mole toabout 20 moles alkali metal compound per mole cyclopentadienyl-typegroup, preferably about 0.2 mole to about 10 moles, and more preferablyabout 0.2 moles to about 5 moles alkali metal compound per molecyclopentadienyl-type group.

Suitable transition metal-containing compounds for preparing thepolymeric metallocene include titanium tetrachloride, zirconiumtetrachloride, hafnium tetrachloride, vanadium tetrachloride, titaniumtetrabromide, zirconium tetrabromide, hafnium tetrabromide, vanadiumtetrabromide, titanium tetraiodide, zirconium tetrabromide, hafniumtetrabromide, vanadium tetrabromide, zirconium tetramethoxide, titaniumtetramethoxide, hafnium tetramethoxide, vanadium tetramethoxide,zirconium tetraethoxide, titanium tetraethoxide, hafnium tetraethoxide,vanadium tetraethoxide, cyclopentadienylzirconium trichloride,cyclopentadienyltitanium trichloride, cyclopentadienylhafniumtrichloride, cyclopentadienylvanadium trichloride,pentamethylcyclopentadienylzirconium trichloride,pentamethylcyclopentadienyltitanium trichloride,pentamethylcyclopentadienylhafnium trichloride,pentamethylcyclopentadienylvanadium trichloride, indenylzirconiumtrichloride, and indenyltitanium trichoride. Zirconium-containing andtitanium-containing compounds are preferred and zirconium tetrachlorideand cyclopentadienylzirconium trichloride are especially preferred.

In preparing the polymeric metallocene, the transition metal-containingcompound is generally present in an amount in the range of from about0.1 mole to about 20 moles transition metal-containing compound per molecyclopentadienyl-type group, preferably about 0.2 mole to about 10moles, and more preferably about 0.5 moles to about 5 moles per molecyclopentadienyl-type group.

The polymeric ligand, the alkali metal compound, and the transitionmetal-containing compound are generally reacted at a temperature in therange of from about -80° C. to about 150° C., preferably from about -40°C. to about 100° C., and more preferably from 0° C. to 50° C.

Preferably the polymeric ligand and the alkali metal compound arecontacted first, prior to contacting with the transitionmetal-containing compound. Typically the reactions will be conducted ina diluent such as tetrahydrofuran, pentane, or diethylether.

In another embodiment, polymeric metallocenes are represented by theformula [Q"MX_(m) ]_(n) wherein Q" is a unit containing at least onefluorenyl-type group, M is a transition metal, each X is individually ahydrocarbyl group containing 1 to 20 carbon atoms, an alkoxy groupcontaining 1 to 12 carbon atoms, an aryloxy group containing 6 to 20carbon atoms, a halide, or hydride, m is 2 or 3, and wherein n is1-5000, preferably 3-1000. Preferably X is a halide or acyclopentadienyl-type group.

Catalyst Systems

The polymeric metallocenes can be used in combination with a suitablecocatalyst to produce catalyst systems for the polymerization ofolefins. Examples of suitable cocatalysts include any of thoseorganometallic cocatalysts which have in the past been employed inconjunction with transition metal-containing olefin polymerizationcatalysts. Some typical examples include organometallic compounds ofmetals of Groups IA, IIA, and IIIB of the Periodic Table. Examples ofsuch compounds include organometallic halide compounds, organometallichydrides, and metal hydrides. Some specific examples includetriethylaluminum, tri-isobutylaluminum, diethylaluminum chloride,diethylaluminum hydride, and the like. Other examples of knowncocatalysts include the use of compounds capable of forming a stablenon-coordinating counter anion, such as disclosed in U.S. Pat. No.5,155,080, e.g. using triphenyl carbeniumtetrakis(pentafluorophenyl)boronate or tris(pentaflurophenyl)boron.Another example would be the use of a mixture of trimethylaluminum anddimethylfluoroaluminum such as disclosed by Zambelli et, Macromolecules,22, 2186 (1989).

Currently, organoaluminoxane cocatalysts are the preferred cocatalysts.Various techniques are known for making organoaluminoxanes. Onetechnique involves the controlled addition of water to atrialkylaluminum. Another technique involves combining atrialkylaluminum and a hydrocarbon with a compound containing water ofadsorption or a salt containing water of crystallization. Many suitableorganoaluminoxanes are commercially available.

Typically the organoaluminoxanes comprise oligomeric, linear and/orcyclic hydrocarbyl aluminoxanes having repeating units of the formula##STR1## wherein each R" is a hydrocarbyl group, preferably an alkylgroup containing 1-8 carbon atoms, x is 2 to 50, preferably 4 to 40, andmore preferably 10 to 40. Typically R" is predominantly methyl or ethyl.Preferably at least about 30 mole percent of the repeating groups havean R which is methyl, more preferably at least 50 mole percent, andstill more preferably at least 70 mole percent. Generally in thepreparation of an organoaluminoxane, a mixture of linear and cycliccompounds is obtained. Organoaluminoxanes are commercially available inthe form of hydrocarbon solutions, generally aromatic hydrocarbonsolutions.

An organoaluminoxy product can be prepared by reacting anorganoaluminoxane and an oxygen-containing compound selected from thegroup consisting of organo boroxines, organic boranes, organicperoxides, alkylene oxides, and organic carbonates. Organo boroxines arepreferred. One such method is disclosed in U.S. Pat. No. 5,354,721, thedisclosure of which is incorporated herein by reference.

The amount of organoaluminoxane relative to the polymeric metalloceneemployed in the catalyst system can vary broadly depending upon theparticular catalyst selected and the results desired. Typically, theorganoaluminoxane is present in the amount of about 0.5 moles to about10,000 moles aluminum per mole of metal in the polymeric metallocene,preferably about 10 moles to about 5,000 moles, and more preferably 50moles to 5,000 moles.

The polymeric metallocene and the cocatalyst are generally contacted inthe presence of a solvent or a diluent. Typical diluents include, forexample, toluene, tetrahydrofuran, dichloromethane, heptane, hexane,benzene, and diethylether.

Polymerization Processes

A variety of olefin compounds are suitable for use as monomers in thepolymerization process of the present invention. Olefins which can beemployed include linear, branched, and cyclic aliphatic olefins. Whilethe invention would appear to be suitable for use with any aliphaticolefin known to be employed with metallocenes, those olefins having 2 to18 carbon atoms are most often used. Ethylene and propylene areespecially preferred. Often a second or third olefin (comonomer) havingfrom 2 to 12 carbon atoms, preferably from 4 to 10 carbon atoms can beemployed. Typical comonomers include propylene, 1-butene,3-methyl-i-butene, 1-pentene, 4-methyl-1-pentene, 2-pentene, 1-hexene,2-hexene, cyclohexene, 1-heptene, and dienes such as butadiene. Ofthese, 1-hexene is preferred.

The polymerization processes according to the present invention can beperformed either batchwise or continuously. The olefin, polymericmetallocene, and organoaluminoxane cocatalyst can be contacted in anyorder. It is preferred that the polymeric metallocene and theorganoaluminoxane are contacted prior to contacting with the olefin. Itmay be advantageous to dry the reaction product before contacting withthe olefin. Generally a diluent such as isobutane is added to thereactor. The reactor is heated to the desired reaction temperature andolefin, such as ethylene or propylene, is then admitted and maintainedat a partial pressure within a range of from about 0.5 MPa to about 5.0MPa (70-725 psi) for best results. At the end of the designated reactionperiod, the polymerization reaction is terminated and the unreactedolefin and diluent vented. The reactor can be opened and the polymer canbe collected as a free-flowing white solid and dried to obtain theproduct.

The reaction conditions for contacting the olefin and the catalystsystem can vary broadly depending on the olefin employed, and are thosesufficient to polymerize the olefins. Generally the temperature is inthe range of about 20° C. to about 300° C., preferably in the range of50° C. to 110° C. The pressure is generally in the range of from about0.5 MPa to about 5.0 MPa (70-725 psi).

The present invention is particularly useful in a gas phase particleform or slurry type polymerization. A particularly preferred typeparticle form polymerization involves a continuous loop reactor which iscontinuously charged with suitable quantities of diluent, catalystsystem, and polymerizable compounds in any desirable order. Typicallythe polymerization will include a higher alpha-olefin comonomer andoptionally hydrogen. Generally the particle form polymerization isconducted at a temperature in the range of about 50° C. to about 110°C., although higher and lower temperatures can be used. The reactionproduct can be continuously withdrawn and the polymer recovered asappropriate, generally by flashing the diluent and unreacted monomersand drying the resulting polymer.

The olefin polymers made with the present invention are useful inpreparing articles prepared by conventional polyolefin processingtechniques, such as injection molding, rotational molding, extrusion offilm, pipe extrusion, and blow molding.

The following examples serve to show the present invention in detail byway of illustration and not by way of limitation.

EXAMPLES

Examples 1-4 present inventive polymeric ligands, polymericmetallocenes, catalyst systems, and their preparation.

Examples 5-6 demonstrate the effectiveness of the inventive polymericmetallocenes in catalyst systems for the polymerization of olefins.

EXAMPLE 1 Synthesis of 2-vinylfluorene

In the following examples, the general procedure described by K. Wong,in Polym. Bul. 1982, 8, 411 for preparing 2-vinylfluorene was followed.In 400 mL ethanol, 46.8 g (0.23 mol) 2-acetylfluorene, (prepared asdescribed in Chem. Abstr. 1965, 62:6443h, also available from AldrichChemical Co., Inc., Milwaukee, Wisc. 53233) and 8.70 g (0.23 mol) sodiumborohydride were refluxed for 2 hours. Then the reaction mixture wasconcentrated by evaporation under vacuum. The residue was taken up in300 mL diethyl ether and washed three times with 250 mL water. Theorganic phase was dried over sodium sulfate and concentrated byevaporation under vacuum. The yield was 45.9 g2-(1-hydroxyethyl)fluorene (97%) in the form of a slightly yellow solid.Then 45.8 g (0.22 mol) 2-(1-hydroxyethyl)fluorene and 2.10 g (0.011 mol)p-toluenesulfonyl chloride in 600 mL toluene were refluxed for 3 hours.The solvent was evaporated under vacuum, the residue was filtered withpentane on alumina B and silica gel 60 and brought to -30° forcrystallization. The thus prepared 2-vinylfluorene precipitated as awhite, crystalline solid. The yield was 16.9 g of 2-vinylfluorene (40%).

Polymeric Ligand A

Radical polymerization of 2-vinylfluorene

To 3.00 g (15.6 mmol) 2-vinylfluorene in 16 mL toluene, 0.13 g (0.8mmol) of azobisisobutyronitrile (AIBN) was added with string. Thereaction continued for 3 days at 90° C. The toluene soluble polymer wasprecipitated with cold methanol. The thus produced polymeric ligand wasthen purified by double reprecipitation from benzene and dried overnightat room temperature under vacuum. The yield was 60-70% of polymericligand A. Polymeric ligand A was employed in preparing the polymericmetallocene AA.

Polymeric Ligands B-F

Radical Copolymerization of 2-vinylfluorene and styrene

Reaction mixtures of 2-vinylfluorene and styrene were stirred with AIBNin solution in toluene for 3 days at 90° C. The relative ratios of2-vinylfluorene to styrene were 1:1, 1:10, 1:20, 1:50, and 1:100,polymeric ligands B-F respectively. A typical example of thepolymerizations was conducted by reacting 1.92 g (10 mmol) 2-vinylfluorene, 10.42 g (100 mmol) styrene, and 0.90 g (5.5 mmol) AIBN in 110mL toluene for 3 days at 90° C. The toluene soluble polymers wereprecipitated with cold methanol. The thus produced polymeric ligandswere then purified by double reprecipitation from benzene and driedovernight at room temperature under vacuum. The yield was 40-70% ofpolymeric ligands B, C, D, E, and F. The polymeric ligands B-F wereemployed in preparing polymeric metallocenes BB, CC, DD, EE, and FFrespectively.

In the table below:

Ligand is the polymeric ligand.

Fluorene/Styrene employed is the molar ratio of 2-vinylfluorene tostyrene employed.

Fluorene/Styrene composition is the molar ratio of fluorene to styrenein the final polymeric composition.

M_(n) is the number average molecular weight of the polymeric ligand.

M_(w) is the weight average molecular weight of the polymeric ligand.

                  TABLE 1                                                         ______________________________________                                              Fluorene/Styrene                                                                           Fluorene/Styrene                                           Ligand                                                                              employed     composition  M.sub.n                                                                             M.sub.w                                 ______________________________________                                        A     1:0          1:0          3000   9400                                   B     1:1          1:1.1        3500  15200                                   C     1:10         1:16         6200  16200                                   D     1:20         1:28.6       3300   5800                                   E     1:50         1:45.6       6500  13600                                   F      1:100       1:86.2       6700  21200                                   ______________________________________                                    

Polymeric Metallocenes AA-FF

The above prepared polymeric ligands A-F were individually suspended inpentane and mixed with an equimolar quantity of n-butylrithium (1.6M inhexane). The mixtures were stirred for 24 hours at room temperature. Thesupernatant was decanted, and each polymer was washed three times with50 mL of pentane. Each washed polymer was combined with 50 mL pentaneand an equimolar quantity of cyclopentadienylzirconium trichloride. Eachreaction mixture was stirred for 24 hours at room temperature and thesupernatant was then decanted. The thus produced polymeric metallocenesAA-FF were washed three times with 50 mL pentane and dried overnight atroom temperature under vacuum.

EXAMPLE 2 Polymeric Ligand G

Alkylating Polymerization of fluorene

To 10.00 g (0.06 mol) fluorene dissolved in 40 mL (0.53 mol)chloromethyl methyl ether, 32.72 g (0.24 mol) zinc(II) chloride wasadded with cooling in ice. The suspension was stirred for 30 minutes atroom temperature. The mixture was slowly poured into 200 mL 10% KOH inmethanol. The supernatant was decanted and the precipitated polyfluorenewas washed five times with 100 mL methanol in water. The residue wasstirred two times for 1 hour in 100 mL acetone. Upon filtering, ayellow-beige colored powder was recovered and then dried under vacuum atroom temperature. The yield was 58% of polymeric ligand G which wasemployed in preparing the polymeric metallocene GG.

Polymeric Metallocene GG

To 1.20 g of the above prepared polymeric ligand G in 30 mL diethylether, was added 5.0 mL (8.0 mmol) n-butyllithium (1.6 M in hexane) withstirring. The reaction mixture was stirred overnight at roomtemperature. The supernatant was decanted and the thus producedpolymeric ligand was washed three times with 30 mL diethyl ether. Thenthe polymeric ligand was combined with 40 mL diethyl ether and 1.50 g(5.7 mmol) cyclopentadienylzirconium trichloride. The reaction mixturewas stirred for 24 hours at room temperature. The supernatant wasdecanted and the polymeric metallocene GG was washed three times with 30mL diethyl ether and dried overnight at room temperature under highvacuum.

EXAMPLE 3 Synthesis of the Bridged Monomer1-(9-(2-vinylfluorenyl)-2-(9-fluorenyl)ethane

To 1.15 g (6.0 mmol) 2-vinylfluorene in 100 mL diethyl ether was added3.75 mL (6.0 mmol) n-butyllithium (1.6M in hexane). The reaction mixturewas stirred for 4 hours at room temperature. Then 1.64 g (6.0 mmol)1-bromo-2-(9-fluorenyl)ethane was added and the mixture was stirred for14 hours at room temperature. The precipitate was removed by filtration,washed with methanol, filtered with pentane using silica gel 60, andconcentrated by evaporation under vacuum. The yield was 1.69 g (73%)1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane as a colorless solid.

Bridged Polymeric Ligand HPoly[1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane]

To 0.31 g (2.1 mmol) 1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane in50 mL diethyl ether, was added 2.63 mL (4.2 mmol) n-butyllithium (1.6Min hexane). The reaction mixture was stirred overnight at roomtemperature to produce the polymeric ligand H which was employed in thepolymerization of the polymeric metallocene HH.

Polymeric Metallocene HH

Poly[1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane zirconiumdichloride]

To the reaction mixture containing polymeric ligand H, was added 0.49 gzirconium tetrachloride. The mixture was stirred overnight at roomtemperature. The solvent was removed by evaporation under vacuum. Thethus produced red solidpoly[1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane zirconiumdichloride] was extracted with methylene chloride, and then the solventwas removed by evaporation under vacuum to produce the polymericmetallocene HH.

Polymeric Ligand I

Copolymerization of 1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane andstyrene

The following compounds were combined in 17 mL toluene and stirred for 3days at 90° C.; 0.30 g (0.8 mmol)1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane, 1.84 mL styrene, and0.14 g (0.84 mmol) AIBN. The toluene-soluble copolymer was precipitatedin cold methanol, purified by double reprecipitation form benzene anddried at room temperature under vacuum. The yield was 40-50% polymericligand poly[styrene/1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane]. Inthe Table below:

Ligand is the polymeric ligand.

Fluorene/Styrene employed is the molar ratio of 2-vinylfluorene tostyrene employed.

Fluorene/Styrene composition is the molar ratio of fluorene to styrenein the final polymeric composition.

M_(n) is the number average molecular weight of the polymeric ligand.

M_(w) is the weight average molecular weight of the polymeric ligand.

                  TABLE 2                                                         ______________________________________                                               Fluorene/Styrene                                                                           Fluorene/Styrene                                          Ligand employed     composition  M.sub.n                                                                             M.sub.w                                ______________________________________                                        I      1:20         1:26.4       1700  5100                                   ______________________________________                                    

Polymeric Metallocene II

Synthesis of poly[styrene/1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethanezirconium dichloride]

To 0.70 g (0.8 mmol)styrene/1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane in 20 mL pentanewas added 5.0 mL (0.8 mmol) n-butyllithium. The mixture was stirred for24 hours at room temperature. The supernatant was decanted and thepolymer washed three times with 30 mL pentane. Then 30 mL pentane and0.70 g (3.0 mmol) zirconium tetrachloride. The reaction mixture wasstirred overnight at room temperature. The supernatant was decanted andthe orange polymer was washed three times with 30 mL pentane and driedat room temperature under vacuum. The yield was 1.08 gstyrene/1-(9-(2-vinyl)fluorenyl)-2-(9-fluorenyl)ethane zirconiumdichloride, polymeric metallocene II.

EXAMPLE 4 Polymeric Ligands J-N

Cationic Polymerization of 2-vinylfluorene

At a temperature of -78° C., 1.92 g (10.0 mmol) 2-vinylfluorene in 30 mLmethylene chloride and 0.60 mL (5.0 mmol) boron trifluoride etheratewere combined. The mixture was stirred overnight at -30° C. Theprecipitated polymer was separated by filtration, dissolved in benzene,precipitated in cold methanol, reprecipitated from benzene, and driedovernight at room temperature under vacuum. The yield of polymericligand J was 70-80%.

Cationic copolymerization of 2-vinylfluorene and styrene

The 2-vinylfluorene and styrene were stirred overnight with 50 mol %boron trifluoride etherate in methylene chloride at -30° C. The polymersinsoluble in methylene chloride were separated by filtration, dissolvedin benzene, precipitated in cold methanol, purified by reprecipitationfrom benzene and dried under vacuum at room temperature. The yield ofpolymeric ligands K-N was 60-75%.

In the Table below:

Ligand is the polymeric ligand.

Fluorene/Styrene employed is the molar ratio of 2-vinylfluorene tostyrene employed.

Fluorene/Styrene composition is the molar ratio of fluorene to styrenein the final polymeric composition.

M_(n) is the number average molecular weight of the polymeric ligand.

M_(w) is the weight average molecular weight of the polymeric ligand.

                  TABLE 3                                                         ______________________________________                                              Fluorene/Styrene                                                                           Fluorene/Styrene                                           Ligand                                                                              employed     composition  M.sub.n                                                                             M.sub.w                                 ______________________________________                                        J     1:0          1:0          5000   7900                                   K     1:1          1:1.2        4500  16400                                   L     1:10         1:3.8        8500  29300                                   M     1:50         1:11.1       9300  23100                                   N      1:100       1:33.2       11500 30700                                   ______________________________________                                    

EXAMPLE 5 Polymerization of Ethylene

The polymeric metallocenes were individually suspended in toluene andactivated by the addition of methylaluminoxane (MAO), 30 wt % intoluene, Mw=1100, WITCO) in a 1,000-fold excess.

The polymerizations were carried out in a one liter Buchi laboratoryautoclave. The autoclave was charged with 500 mL pentane, 2 mL MAO, andthe indicated polymeric metallocene. The reactor temperature wasregulated at 60° C. and a constant pressure of 10 bar of ethylene wasapplied. After one hour, the polymerization reaction was interrupted,and the polyethylene was recovered and the yield determined. The resultsare summarized in Table 1.

In the Table below:

Metallocene is the polymeric metallocene in mg.

Polyethylene is the yield of polyethylene in grams.

Activity/M is the grams polyethylene per (gram polymericmetallocenehourbar).

Activity/Zr is the grams polyethylene per (gram zirconiumhourbar).

                  TABLE 4                                                         ______________________________________                                                             Activity/M  Activity/Zr                                  Metallocene mg                                                                          Polyethylene g                                                                           g PE/g M · hr · b                                                       g PE/g Zr · hr ·           ______________________________________                                                                         b                                            AA 4      29.5       738         3400                                         BB 2      14.5       725         4200                                         CC 2      53.0       2650        61000                                        DD 2      55.5       2775        103000                                       EE 28     22.5       80          4600                                         FF 104    16.0       15          1600                                         GG 14     31.0       221         1100                                         HH 1      34.5       3455        20600                                        II 70     7.5        11          390                                          ______________________________________                                    

EXAMPLE 6 Polymerization of Propylene

To a one liter Buchi autoclave was charged 2 mL MAO (30 wt % in toluene)and 500 mL propylene. The contents were stirred for 30 minutes at 20° C.in order to dry the propylene. To the autoclave was added 11.9 mgpolymeric metallocene HH suspended in toluene and mixed with theappropriate quantity of MAO. The autoclave was regulated to 60° C. forone hour. The yield of polypropylene was 3.4 g and the activity of themetallocene was 285 g polypropylene/(g metallocenehour).

What is claimed is:
 1. A catalyst composition produced by combining anorganoaluminoxane cocatalyst and a polymeric metallocene catalyst, saidpolymeric metallocene catalyst being prepared by(1) forming afluorenyl-containing polymer by(a) polymerizing a 2-vinyl fluorenecompound or (b) polymerizing a fluorene compound by reacting it withchloromethylmethylether in the presence of zinc dichloride or aluminumtrichloride; (2) reacting the fluorenyl-containing polymer with analkali metal compound; and (3) reacting the product of step (2) with atransition metal-containing compound.
 2. A catalyst compositionaccording to claim 1 wherein the fluorenyl containing polymer isproduced by polymerizing a 2-vinylfluorene compound.
 3. A catalystcomposition according to claim 2 wherein the 2-vinylfluorene compound iscopolymerized with styrene.
 4. A catalyst composition according to claim3 wherein the 2-vinylfluorene compound employed is 2-vinylfluorene.
 5. Acatalyst composition according to claim 4 wherein zirconiumtetrachloride is used as the transition metal-containing compound.
 6. Acatalyst composition according to claim 4 wherein the transitionmetal-containing compound that is employed is cyclopentadienyl zirconiumtrichloride.
 7. A catalyst composition according to claim 3 wherein the2-vinylfluorene compound is a vinylfluorene compound having acyclodienyl group attached to the fluorene by a bridging group.
 8. Acatalyst composition according to claim 2 wherein thefluorenyl-containing polymer is prepared by the homopolymerization of a2-vinylfluorene compound.
 9. A catalyst composition according to claim 8wherein the transition metal-containing compound employed in step (3) isselected from the group consisting of fluorenyl zirconium dichloride,indenyl zirconium trichloride, and cyclopentadienyl zirconiumdichloride.
 10. A catalyst composition according to claim 8 wherein thetransition metal-containing compound used in step (3) iscyclopentadienyl zirconium trichloride.
 11. A catalyst compositionaccording to claim 8 wherein the 2-vinylfluorene compound is avinylfluorene compound having a cyclodienyl group attached to thefluorene by a bridging group.
 12. A catalyst composition according toclaim 11 wherein the fluorenyl-containing polymer is produced by thehomopolymerization of 1-(9-(2-vinyl) fluorenyl)-2-(9-fluorenyl) ethane.13. A catalyst composition according to claim 12 wherein the transitionmetal-containing compound employed in step (3) is zirconiumtetrachloride.
 14. A catalyst composition according to claim 1 whereinsaid organoaluminoxane cocatalyst has repeating units of the formula##STR2## wherein each R' is a hydrocarbyl group containing 1-8 carbonatoms, and x is 2 to
 50. 15. A catalyst system according to claimwherein the organoaluminoxane cocatalyst is methylaluminoxane.